Multiplex ethylene copolymer, process for preparation thereof and cured product thereof

ABSTRACT

Disclosed is a multiplex ethylene coplymer comprising (a) 50 to 94.8 mole % of units derived from ethylene, which are represented by the following formula (I): 
     
         --CH.sub.2 --CH.sub.2 --                                   (I) 
    
     (b) 5 to 45 mole % of units derived from a monomer selected from alkyl acrylates, alkyl methacrylates, vinyl carboxylates and isopropenyl carboxylates, which are represented by the following formula (II): ##STR1## wherein R 1  stands for a hydrogen atom or a methyl group, and X is ##STR2## in which R 2  and R 3  stand for an alkyl group having 1 to 10 carbon atoms), and (c) 0.2 to 5 mole % of units derived from a monomer having a radical-polymerizable ethylenic double bond and at least one carbon-to-carbon double bond which is different from a double bond of an aromatic nucleus. This ethylene copolymer can be easily cured, and the cured copolymer is a rubber having excellent oil resistance and heat resistance. 
     This multiplex ethylene copolymer can be obtained by copolymerizing a monomer forming the units (a) with a monomer forming the units (b) and (c&#39;) a monomer having a radical-polymerizable ethylenic double bond and an acid anhydride group, a carboxyl group and/or an epoxy group, and modifying the obtained copolymer with a low-molecular-weight modifier selected from unsaturated amines and unsaturated alcohols having at least one carbon-to-carbon double bond different from a double bond of an aromatic nucleus (when a radical-polymerizable monomer having an epoxy group is used, the low-molecular-weight modifier may be an unsaturated carboxylic acid having at least one carbon-to-carbon double bond different from a double bond of an aromatic nucleus).

This is a continuation of application No. 07/098,767 filed Sept. 17,1987, now abandoned, which is a continuation of U.S. Ser. No.06/824,686, filed Jan. 21, 1986 now abandoned.

DESCRIPTION

1. Technical Field

The present invention relates to a curable ethylene copolymer, a processfor the preparation thereof and a cured product thereof. Moreparticularly, the present invention relates to a curable ethylenecopolymer which can provide, by ordinary sulfur curing or peroxidecuring, an elastomer having excellent heat resistance, solventresistance, weatherability, ultraviolet ray resistance, ozone resistanceand low-temperature characteristics, a process for the preparationthereof, and a cured product thereof obtained by sulfur curing orperoxide curing.

2. Background Art

Rubbers excellent in such physical properties as heat resistance and oilresistance are now desired mainly in the field of automobile parts. Asone elastomer meeting the requirements of the physical properties, acopolymer of ethylene with a monomer having a polar group, such as anacrylic acid ester, is manufactured on an industrial scale and isutilized in various fields. Various preparation processes and physicalproperties are known in connection with this elastomer.

For example, U.S. Pat. No. 3,956,248 discloses a process in which analternating copolymer of ethylene with an alkyl acrylate and ahalogen-containing acrylate is prepared in the presence of a specialcatalyst. It is stated that according to this process, an elastomerhaving excellent oil resistance and heat resistance can be obtained bycrosslinking with a peroxide or curing with hexamethylene diaminecarbamate.

U.S. Pat. No. 3,883,472 discloses a process in which anacrylate/1,4-butenedionic acid monoester copolymer or a terpolymerthereof with ethylene is crosslinked with a polyamine and a curingpromoter. Furthermore, U.S. Pat. No. 3,904,588 discloses a process inwhich a similar terpolymer is cured with hexamethylene diaminecarbamate.

Moreover, U.S. Pat. No. 4,304,887 and U.S. Pat. No. 4,307,007 proposethat a chromium (III) compound or a phosphate is added as an agent forimproving the green strength or an anti-blocking agent to a terpolymeras described above.

Moreover, U.S. Pat. No. 4,399,263 proposes the combined use of amonoamine with a polyamine for improving the storage stability orscorching property.

Furthermore, U.S. Pat. No. 4,412,043 proposes a process in which anethylene/acrylate/4-dialkylamino-4-oxo-2-butanoic acid copolymerobtained by reacting a terpolymer such an ethylene/acrylate/maleicanhydride terpolymer with a dialkylamine is cured with a diamine or apolyamine.

As is apparent from the foregoing description, ethylene/acrylatecopolymer elastomers are prepared by using carboxyl groups present inthe polymer chain as curing sites and curing them with a diamine, apolyamine or a derivative thereof. A monoamine is added to reduce theamount of remaining carboxyl groups for improving the storage stabilityor scorching property. Accordingly, in the conventional techniques,trials have not been made to introduce carbon-to-carbon double bonds assulfur-curable sites into the polymer chain by copolymerization ormodification or to cure such a copolymer with sulfur.

Since crosslinking sites are carboxyl groups in the above-mentionedcurable copolymer, the copolymer can be crosslinked with a diamine orwith an ion. However, for example, in the case of a uncrosslinked rubbercomposition formed by kneading a diamine or a polyamine into thiscopolymer, crosslinking reaction is readily advanced even at normaltemperature and hence, the storage stability is poor. Moreover,scorching is readily caused during the crosslinking operation.

We carried out research with a view to providing an ethylene copolymerreadily curable with sulfur by using the conventional equipment andtechnique, and as the result, it has been found that by introducingcarbon-to-carbon double bonds as sulfur-curing sites into the polymerchain, there can be obtained a rubber which can be easily cured withsulfur to provide a cured product having excellent oil resistance andheat resistance.

DISCLOSURE OF THE INVENTION

In accordance with one aspect of the present invention, there isprovided a multiplex ethylene copolymer comprising (a) 50 to 94.8 mole%of units derived from ethylene, which are represented by the followingformula (I):

    --CH.sub.2 --CH.sub.2 --                                   (I)

(b) 5 to 45 mole% of units derived from a monomer selected from alkylacrylates, alkyl methacrylates, vinyl carboxylates and isopropenylcarboxylates, which are represented by the following formula (II):##STR3## wherein R₁ stands for a hydrogen atom or a methyl group, and Xis ##STR4## (in which R₂ and R₃ stand for an alkyl group having 1 to 10carbon atoms), and (c) 0.2 to 5 mole% of units derived from a monomerhaving a radical-polymerizable ethylenic double bond and at least onecarbon-to-carbon double bond which is different from a double bond of anaromatic nucleus.

In accordance with another aspect of the present invention, there isprovided a process for the preparation of a modified multiplex ethylenecopolymer, which comprises modifying a multiplex ethylene copolymercomprising (a) 50 to 94.8 mole% of units derived from ethylene, whichare represented by the following formula (I):

    --CH.sub.2 --CH.sub.2 --                                   (I)

(b) 5 to 45 mole% of units derived from a monomer selected from alkylacrylates, alkyl methacrylates, vinyl carboxylates and isopropenylcarboxylates, which are represented by the following formula (II):##STR5## wherein R₁ stands for a hydrogen atom or a methyl group, and Xis ##STR6## (in which R₂ and R₃ stand for an alkyl group having 1 to 10carbon atoms), and (c) 0.2 to 5 mole% of units derived from aradical-polymerizable monomer containing an acid anhydride group, acarboxyl group or an epoxy group with at least one low-molecular-weightmodifier selected from unsaturated amines and unsaturated alcoholshaving at least one carbon-to-carbon double bond different from a doublebond of an aromatic nucleus (with the proviso that when aradical-polymerizable monomer containing an epoxy group is used, thelow-molecular-weight modifier may be an unsaturated carboxylic acidhaving at least one carbon-to-carbon double bond different from a doublebond of an aromatic nucleus).

The above-mentioned multiplex ethylene copolymer is cured with sulfurand/or a sulfur donor or crosslinked with a peroxide to form a rubberycopolymer having excellent oil resistance and heat resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

In the multiplex ethylene copolymer of the present invention, the amountof ethylene units represented by the formula (I) is 50 to 94.8 mole%,preferably 53 to 86.6 mole%. If the amount of ethylene units representedby the formula (I) is too small, the low-temperature characteristics ofthe cured product are degraded, and if the amount of ethylene unitsrepresented by the formula (I) is too large, the permanent elongation orcompression permanent strain of the cured product is increased and therubbery elasticity is decreased.

In the multiplex ethylene copolymer of the present invention, the unitsrepresented by the formula (II) are derived from a monomer selected fromalkyl acrylates and alkyl methacrylates having 1 to 10 carbon atoms inthe alkyl group and vinyl esters and isopropenyl esters of aliphaticmonocarboxylic acids having 2 to 11 carbon atoms. The amount of theunits represented by the formula (II) is 5 to 45 mole%, preferably 10 to45 mole%, especially preferably 13 to 45 mole%. If the amount of theunits represented by the formula (II) is smaller than 5 mole%, therubbery elasticity of the cured product is lost and the tensionpermanent set or compression permanent set is increased. In contrast, ifthe amount of the units represented by the formula (II) exceeds 45mole%, the low-temperature brittleness characteristics of the curedproduct are degraded.

In the multiplex ethylene copolymer of the present invention, as theunits derived from a monomer having a radical-polymerizable ethylenicdouble bond and at least one carbon-to-carbon double bond different froma double bond of an aromatic nucleus, there are generally used unitsderived from monomers containing at least one atom selected from oxygenand nitrogen in the molecule. Preferred units are represented by thefollowing formula (III): ##STR7## wherein R₄ stands for a hydrogen atomor ##STR8## (in which R₆ stands for a hydrogen atom or an alkyl grouphaving 1 to 6 carbon atoms), R₇ stands for a hydrogen atom or a methylgroup, R₈ stands for a hydrocarbon residue having up to 40 carbon atoms,which contains at least one carbon-to-carbon double bond different froma double bond of an aromatic nucleus, and Y is a divalent group selectedfrom divalent groups represented by the following formulae (IV) through(IX): ##STR9## wherein Q in the formulae (VIII) and (IX) is --NR₉ --,##STR10## and R₉ in the formula (VII) and the definition of Q stands fora hydrocarbon residue having up to 40 carbon atoms, which contains atleast one carbon-to-carbon double bond different from a double bond ofan aromatic nucleus, an alkyl, aryl or aralkyl group having up to 20carbon atoms or a hydrogen atom.

More preferable units are selected from units represented by thefollowing formulae (X), (XI), (XII) and (XVI): ##STR11## wherein R₇ andR₁₀ stand for a hydrogen atom or a methyl group, R₁₁ stands for ahydrocarbon residue having 6 to 20 carbon atoms, which contains acarbon-to-carbon double bond different from a double bond of an aromaticnucleus, R₁₂ stands for a hydrogen atom or an alkyl group having 1 to 10carbon atoms, and Z and Z' independently stand for ##STR12##

The units derived from the radical-polymerizable monomer are containedin the copolymer in an amount of 0.2 to 5 mole%, preferably 0.5 to 5mole%. If the amount of the units is smaller than 0.2 mole%, even whencuring is sufficiently carried out, a cured product having desiredrubbery elasticity and heat resistance cannot be obtained. In contrast,if the amount of the units exceeds 5 mole%, the softness of the curedproduct is degraded and the intended rubbery properties cannot beobtained.

The multiplex ethylene copolymer may contain units derived from othermonomer in addition to the units represented by the formula (I), theunits represented by the formula (II) and the units derived from theradical-polymerizable monomer. The amount of the units derived fromother monomer is up to 20 mole%.

The multiplex ethylene copolymer of the present invention can beprepared according to processes described below, which are roughlydivided into two types. According to the first process, ethylene formingunits represented by the formula (I) is copolymerized with a monomerforming units represented by the formula (II) and a monomer comprising aradical-polymerizable ethylenic double bond and at least onecarbon-to-carbon double bond different from a double bond of an aromaticnucleus According to the second process, ethylene forming unitsrepresented by the formula (I) is copolymerized with a monomer formingunits represented by the formula (II) and a monomer having aradical-polymerizable ethylenic double bond and a functional groupselected from an acid anhydride group, a carboxyl group and an epoxygroup to form a multiplex ethylene copolymer having such a functionalgroup, and the copolymer is modified with a low-molecular-weightmodifier having an amino group, hydroxyl group or carboxyl group capableof reacting with the functional group to introduce a carbon-to-carbondouble bond as the curing site into the side chain of the polymer.According to a modification of the second process, ethylene formingunits represented by the formula (I) is copolymerized with a monomerforming units represented by the formula (II), the obtained copolymer isgraft-polymerized with a monomer having a functional group selected froman acid anhydride group, a carboxyl group and an epoxy group, and thegrafted copolymer is modified with a low-molecular-weight modifier asdescribed above.

In the first process for the preparation of the multiplex ethylenecopolymer, (i) ethylene forming units represented by the formula (I) iscopolymerized with (ii) a monomer forming units represented by theformula (II) (that is, a monomer selected from alkyl acrylates and alkylmethacrylates having 1 to 10 carbon atoms and vinyl esters andisopropenyl esters of aliphatic monocarboxylic acids having 2 to 11carbon atoms) and (iii) a monomer having a radical-polymerizableethylenic double bond and at least one carbon-to-carbon double bonddifferent from a double bond of an aromatic nucleus, preferably amonomer represented by the following formula (III'): ##STR13## whereinR₄, R₇, Y and R₈ are as defined above in the formula (III).

It is especially preferred that the radical-polymerizable monomer (iii)be selected from monomers represented by the following formulae (X'),(XI'), (XII') and (XVI'): ##STR14## wherein R₇, R₁₀, R₁₂, Z and Z' areas defined above in the formulae (X), (XI), (XII) and (XVI).

As examples of the radical-polymerizable monomers represented by theformulae (III'), (X'), (XI'), (XII') and (XVI'), there can be mentionedthe following compounds (a) through (h).

(a) Acrylic acid esters or methacrylic acid esters comprising as thealcohol component an alcohol having at least one carbon-to-carbon doublebond different from a double bond of an aromatic nucleus and up to 40carbon atoms, in which Y in the formula (III') is equal to the formula(IV), such as oleyl acrylate and oleyl methacrylate.

(b) Monoesters and diesters of maleic acid or methylmaleic acid(citraconic acid) having as the alcohol component an alcohol having atleast one carbon-to-carbon double bond different from a double bond ofan aromatic nucleus and up to 40 carbon atoms, in which Y in the formula(III') is equal to the formula (IV), such as oleyl maleate.

(c) Acrylamides or methacrylamides having as the amine component anamine having at least one carbon-to-carbon double bond different from adouble bond of an aromatic nucleus and up to 40 carbon atoms, in which Yin the formula (III') is equal to the formula (VII), such asN-9-octadecenyl acrylamide.

(d) Monoamides and diamides of maleic acid or methylmaleic acid(citraconic acid) having as the amine component an amine having at leastone carbon-to-carbon double bond different from a double bond of anaromatic nucleus, in which Y in the formula (III') is equal to theformula (VII), (XI') or (XII"), such as4-octadecenylamino-4-oxo-2-butenoic acid.

(e) Vinyl esters and isopropenyl esters of unsaturated carboxylic acidshaving at least one carbon-to-carbon double bond different from a doublebond of an aromatic nucleus and up to 41 carbon atoms, in which Y in theformula (III') is equal to the formula (V), such as vinyl oleate andvinyl ricinoleate.

(f) Alkenyl, vinyl or isopropenyl ethers having at least onecarbon-to-carbon double bond different from a double bond of an aromaticnucleus and up to 40 carbon atoms, in which Y in the formula (III') isequal to the formula (VI), such as 9-octadecenyl vinyl ether, divinylether and diallyl ether.

(g) Reaction products between glycidyl acrylate or methacrylate and anunsaturated amine, unsaturated alcohol or unsaturated carboxylic acid,in which Y in the formula (III') is equal to the formula (VIII) or (IX).

(h) Imides having at least one carbon-to-carbon double bond differentfrom a double bond of an aromatic nucleus, which corresponds to theformula (XVI'), such as 9-octadecenylmaleimide.

In the above-mentioned first preparation process, the copolymerizationratios of the respective monomers are set so that the ethylene copolymerhaving the above-mentioned composition can be obtained.

As specific examples of the monomer forming the units represented by theformula (II), there can be mentioned methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate,propyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethacrylate, butyl methacrylate, vinyl acetate and vinyl propionate.Methyl methacrylate, methyl acrylate, ethyl acrylate and vinyl acetateare especially preferred.

The copolymerization may be carried out at 50° to 200° C. under 5 to 200kg/cm² in the presence of an organic solvent such as benzene, toluene,hexane or heptane, or at 120° to 260° C. under 500 to 2,500 kg/cm² inthe absence of a solvent. As the polymerization initiator, there may beused t-butyl perpivalate, t-butyl peroxide, 2,5-dimethyl-di-t-butylperoxide, benzoyl peroxide and azobisisobutyronitrile. The contents(mole%) of the structural units (I), (II) and (III) can be controlled byappropriately selecting the ratio of the reacted monomers according tothe kinds of monomers used and the copolymerization reaction conditions,and for example, the melt index (MI) of the copolymer may be adjusted bycontrolling the kind and amount of the polymerization initiatoraccording to the kinds of monomers used and the copolymerizationreaction conditions.

In the second preparation process, at first, ethylene forming the unitsrepresented by the formula (I) is copolymerized with a monomer formingthe units represented by the formula (II) and a radical-polymerizablemonomer having functional group selected from an acid anhydride group, acarboxyl group and an epoxy group to form an ethylene copolymer having afunctional group. Alternately, ethylene forming the units represented bythe formula (I) is copolymerized with a monomer forming the unitsrepresented by the formula (II), and the obtained copolymer isgraft-polymerized with a radical-polymerizable monomer having afunctional group selected from an acid anhydride group, a carboxyl groupand an epoxy group.

As the radical-polymerizable monomer having an acid anhydride group asthe functional group, there can be mentioned maleic anhydride,norbornene-dicarboxylic anhydride and cyclohexene-dicarboxylicanhydride, and maleic anhydride is preferred. As theradical-polymerizable monomer having a carboxyl group as the functionalgroup, there can be mentioned acrylic acid, methacrylic acid, maleicacid, fumaric acid, monomethyl maleate and monoethyl maleate As themonomer having an epoxy group, there can be mentioned glycidyl acrylateand glycidyl methacrylate.

The copolymerization procedures in the second preparation process may bethe same as those in the first preparation process. The graftpolymerization with a monomer such as maleic anhydride may be carriedout in the presence of a radical polymerization initiator by using akneading machine such as a Banbury mixer or a vent type single or twinscrew extruder.

In the second preparation process, the copolymerization ratios of therespective monomers can be set as in the first preparation process. Themonomer forming the units represented by the formula (II) may beselected from the compounds specifically mentioned above with respect tothe first preparation process.

According to a modification of the second process for preparing amultiplex ethylene copolymer comprising the units represented by theformula (I), the units represented by the formula (II) and the unitsderived from a monomer having a carboxyl group, ethylene iscopolymerized with an alkyl acrylate or alkyl methacrylate forming theunits represented by the formula (II), and the units of the formula (II)(possessed by the ester groups) in the obtained copolymer are partiallyhydrolyzed to convert some ester groups to carboxyl groups. Thishydrolysis can be accomplished by treating the copolymer with asaponifying agent such as an alkali metal hydroxide, an alkaline earthmetal hydroxide, an alcoholate, an alkali metal salt of a weakcarboxylic acid or an alkali metal salt of a weak inorganic acid. Thecopolymer treated with the saponifying agent is treated with an acid toeffect neutralization.

The melt index (measured at a temperature of 190° C. and a load of 2.16kg according to JIS K-7210; hereinafter referred to as "MI") of theethylene copolymer is ordinarily 0.01 to 1000 g/10 min, preferably 0.1to 500 g/10 min, especially preferably 0.1 to 300 g/10 min. When acopolymer having an MI smaller than 0.01 g/10 min is used, when sulfur,a sulfur donor or other additive is added for curing, homogeneous mixingis difficult and the moldability is poor.

Then, the copolymer or grafted copolymer is treated with alow-molecular-weight modifier having an amino group and/or a hydroxylgroup (which may have a carboxyl group in addition to the amino groupand/or hydroxyl group when the radical-polymerizable monomer (iii) is amonomer having an epoxy group) and having a carbon-to-carbon double bonddifferent from a double bond of an aromatic nucleus to react it with thefunctional group, whereby carbon-to-carbon double bonds are introducedas the curing sites in the side chains of the polymer.

As the low-molecular-weight modifiers having amino, hydroxyl andcarboxyl groups, there may be used unsaturated amines, unsaturatedalcohols and unsaturated carboxylic acids (in the case where a monomercontaining an epoxy group is used as the radical-polymerizable monomer(iii)) having at least one carbon-to-carbon double bond different from adouble bond of an aromatic nucleus. These modifiers will now bedescribed.

Unsaturated Amine

The unsaturated amine used in the present invention is a compound havingat least one carbon-to-carbon double bond different from a double bondof an aromatic nucleus and an amino group, and a compound represented bythe following general formula is especially preferred: ##STR15## whereinR₁₅ and R₁₆ stand for a hydrogen atom, or at least one of them is ahydrocarbon group having at least one double bond, with the proviso thatthe case where both of them simultaneously stand for a hydrogen atom isexcluded.

In the above general formula, each hydrocarbon group has up to 40 carbonatoms, and a hydrocarbon group having up to 30 carbon atoms, especially1 to 20 carbon atoms, is preferred. Furthermore, an unsaturated aminewhich is liquid or solid at normal temperature or a reaction temperaturedescribed below, is preferred.

As typical instances of the unsaturated amine, there can be mentioned1-amino-9-nonadecene, 1-amino-9-octadecene, 1-amino-7-hexadecene,1-amino-5-pentadecene, 1-amino-4-tetradecene, 1-amino-4-tridecene,1-amino-3-dodecene, 1-amino-2-decene, 1-amino-2-octene,1-amino-2-hexene, aminoethyl acrylate and diallyl amine. Among theseamines, 1-amino-9-octadecene is especially preferred.

Unsaturated Alcohol

The unsaturated alcohol used in the present invention is a compoundhaving at least one double bond different from a double bond of anaromatic nucleus and having a hydroxyl group. The carbon number is up to40, and it is preferred that the carbon number be up to 30, morepreferably up to 25. An aliphatic or aromatic compound having onehydroxyl group is preferred.

As typical instances of the unsaturated alcohol, there can be mentionedunsaturated aliphatic alcohols such as 1-hydroxy-9-octadecene,1-hydroxy-7-heptadecene, 1-hydroxy-5-tetradecene, 1-hydroxy-5-dodecene,1-hydroxy-3-octene, allyl alcohol and hydroxyethyl methacrylate, andunsaturated aromatic alcohols (or phenols) such as p-vinylphenol,vinylhydroxybiphenyl and vinylnaphthol.

Unsaturated Carboxylic Acid

The unsaturated carboxylic acid that can be used in the presentinvention when a monomer containing an epoxy group is used as theradical-polymerizable monomer (iii) is an unsaturated carboxylic acidhaving a carbon-to-carbon double bond different from a double bond of anaromatic nucleus and having 3 to 40 carbon atoms. As typical instances,there can be mentioned acrylic acid, methacrylic acid, oleic acid,linoleic acid, linolenic acid, clupanodonic acid, ricinoleic acid andpimaric acid. Among these acids, methacrylic acid is especiallypreferred.

In the ethylene copolymer, the amount of the low-molecular-weightmodifier such as the unsaturated amine, unsaturated alcohol orunsaturated carboxylic acid is 0.2 to 5.0 mole, preferably 0.2 to 2.0moles, more preferably 0.5 to 2.0 moles, per mole of the total amount ofthe structural units derived from the radical-polymerizable monomerhaving a functional group. If the amount of the low-molecular-weightmodifier is smaller than 0.2 mole per mole of the total amount of thestructural units derived from the radical-polymerizable monomer having afunctional group, a modified ethylene copolymer having a desiredmodifying effect cannot be obtained. On the other hand, if the amount ofthe modifier exceeds 5.0 moles per mole of the total amount of theradical-polymerizable monomer, the unreacted unsaturated amine orunsaturated alcohol remains in the modified ethylene copolymer to causebleeding or smelling. The modification with the low-molecular-weightmodifier is accomplished, for example, according to the followingprocedures.

More specifically, the ethylene copolymer having the above-mentionedspecific structure and the modifier are dissolved in a solvent and thesolution is heated at 50° to 200° C., or the copolymer and modifier arenot dissolved in a solvent but are kneaded at a temperature of at leastthe melting point of the ethylene copolymer but lower than the thermaldecomposition temperature (that is, 120° to 300° C.) for 0.5 to 20minutes (preferably 3 to 15 minutes) by a kneading machine such as aBanbury mixer or a vent type single or twin screw extruder. Note, asmall amount of a catalyst may be used for the modification.

The MI of the modified ethylene copolymer is ordinarily 0.01 to 1000g/10 min, and preferably 0.05 to 50 g/10 min, especially preferably 0.1to 300 g/10 min. If MI of the modified ethylene copolymer is smallerthan 0.01 g/10 min, when the modified copolymer is mixed with additivesdescribed below and, sulfur, sulfur donors, peroxides and curingpromoters, the kneading property is poor and the moldability is degraded

CAPABILITY OF EXPLOITATION IN INDUSTRY

The ethylene copolymer of the present invention may be cured with sulfuror a sulfur donor or crosslinked with a peroxide.

The cured product obtained by curing has a very rich rubbery elasticityand the permanent elongation is lower than 45% at room temperature (20°C.). Furthermore, the weatherability is extremely excellent, and whenthe cured product is allowed to stand at 190° C. for more than 70 hours,the residual ratio of the elongation at break is at least 50%. Moreover,the cured product has an extremely excellent in oil resistance, heatresistance, solvent resistance and low-temperature brittlenessresistance. Accordingly, the cured product is especially suitable forthe production of hoses and packings to be arranged around an automobileengine. Moreover, the cured product is suitable for hoses to be used incold districts and for the soles of boots.

Curing with sulfur or a sulfur donor may be carried out according to thefollowing procedures. Ordinarily, the ethylene copolymer is kneaded withsulfur or a sulfur donor and other additives, for example, a curingassistant such as zinc flower, a filler such as carbon black, titaniumwhile (TiO₂) or calcium carbonate (CaCO₃), a plasticizer such as a fattyacid ester, a polyester type plasticizer or a polybutene oligomer and aparting agent such as stearic acid by using a kneader or the like. As inthe case of ordinary rubbers, kneading is carried out at a temperaturehigher than 30° C. The mixture is molded into a sheet or other optionalintended shape by using a roll, a calender roll or an extruder, and themolded body is steam-cured or press-cured to obtain a cured product.

Sulfur or the sulfur donor is used in an amount of 0.1 to 10 parts byweight per 100 parts by weight of the ethylene copolymer. Curingpromoters customarily used in the art of rubbers, such asaldehyde-ammonia type promoters, aldehyde-amine type promoters, thioureatype promoters, guanidine type promoters, thiazole type promoters,sulfenamide type promoters, thiuram type promoters, dithiocarbamate typepromoters, xanthate type promoters, oxime type promoters and morpholinetype promoters, are ordinarily used as the sulfur donor. As specificexamples, there can be mentioned tetramethylthiuram disulfide,dipentamethylenethiuram tetrasulfide, 2-mercaptobenzothiazole and2-(4'-morpholinodithio)benzothiazole.

Curing with a peroxide may be carried out according to customaryprocedures by using peroxides customarily used, for example, ketoneperoxides such as methylethyl ketone peroxide, diacyl peroxides such asbenzoyl peroxide, hydroperoxides such as t-butyl hydroperoxide, dialkylperoxides such as dicumyl peroxide, and alkyl peresters such as t-butylperacetate. For example, the copolymer is kneaded with a peroxide and acrosslinking assistant in a laboratory plastomill at a temperature lowerthan the decomposition temperature of the crosslinking agent for a shorttime (3 to 40 minutes). The mixture is placed in a mold and crosslinkedat a temperature higher than the decomposition temperature by a press.

The amount of the peroxide used is 0.0005 to 0.02 mole per 100 g of theethylene copolymer. If the crosslinking agent is used in combinationwith the peroxide, the amount of the peroxide used can be reduced andthe physical properties of the cured product can be improved.Ordinarily, 0.0001 to 0.002 mole of the peroxide and 0.5 to 5 g of thecrosslinking agent are used per 100 g of the ethylene copolymer. As thecrosslinking assistant, there can be used, for example, polyfunctionalmonomers such as triallyl isocyanurate, triallyl cyanurate, diallylphthalate, triallyl trimethacrylate and trimethylolpropane methacrylate.

The present invention will now be described in detail with reference tothe following examples that by no means limit the scope of theinvention.

The physical properties of the products obtained in the followingexamples were evaluated according to the following methods.

The melt index (MI) of the ethylene copolymer was measured at atemperature of 190° C. and a load of 2.16 kg according to the method ofJIS K-7210.

The conversion of the unsaturated amine or unsaturated alcohol wascalculated by extracting the modified ethylene copolymer with anon-solvent by using a Soxhlet extractor and determining the amount ofthe unreacted amine or alcohol in the extract by gas chromatography.Similarly, the conversion was calculated by extracting the modifiedethylene copolymer with a non-solvent (carbon tetrachloride/methylalcohol liquid mixture having a volume ratio of 6/4) by using a Soxhletextractor and determining the iodine value of the unreacted unsaturatedamine or unsaturated alcohol in the extract.

The tensile test was carried out according to JIS K-6301. The Shorehardness (A) was measured according to JIS K-6301. The heat resistancewas tested by allowing the sample to stand at a temperature of 190° C.for 79 hours and measuring the elongation according to JIS K-6301. TheIzod impact strength was measured according to ASTM D-256.

The maleic anhydride content was determined by the nuclear magneticresonance and infrared absorption spectrum methods.

EXAMPLES 1 AND 3 AND COMPARATIVE EXAMPLES 1 AND 2

(Preparation of Modified Ethylene Copolymer)

Ethylene was copolymerized with methyl methacrylate and maleic anhydrideaccording to procedures described below. In an autoclave having acapacity of 1 liter and equipped with a stirrer, a monomer mixturecomprising 88.8% by weight of ethylene, 10.9% by weight of methylmethacrylate and 0.3% by weight of maleic anhydride andt-butylperoxy-2-ethyl hexanoate in an amount of 550 ppm based on thewhole monomers were continuously fed and polymerization was continuouslycarried out at a temperature of 153° C. under a pressure of 1,750kg/cm².

Similarly, several ethylene copolymers were prepared by carrying out thepolymerization under conditions shown in Table 1. The obtained resultsare shown in Table 1.

The thus-obtained ethylene copolymers were modified with oleyl amineaccording to procedures described below. Namely, a modifier (see Table2) was added to the ethylene copolymer in an amount of 1 mole or 2 molesper mole of the maleic anhydride units in the copolymer as shown inTable 1, and kneading reaction was carried out at 80° C. and 40 rpm for20 minutes in a laboratory plastomill. The reaction ratio of oleyl aminewith the maleic anhydride units in the copolymer was 64% when oleylamine was added in an equimolar amount or 91% when oleyl amine was addedin an amount of 2 moles per mole of the maleic anhydride units. Otherpolymers were similarly modified.

(Evaluation of Physical Properties)

The thus-obtained modified ethylene copolymer was mixed with a curingagent and a curing assistant at ratios shown in Table 2, and the mixturewas kneaded at 80° C. and 80 rpm for 5 minutes in a laboratoryplastomill and press-cured under curing conditions shown in Table 2.

The physical properties of the obtained cured products are shown inTable 2.

                  TABLE 1                                                         ______________________________________                                                                 Comparative                                                     Example No.   Example No.                                                     1     2       3       1     2                                      ______________________________________                                        Acrylic acid ester*                                                                        MMA     MMA     MMA   MMA   MMA                                  Polymerization tem-                                                                         153     155     220   155   153                                 perature (°C.)                                                         Polymerization pres-                                                                       1750    1680    1850  1780  1650                                 sure (kg/cm.sup.2)                                                            Composition of polymer (mole %)                                               Ethylene     79.1    75.3    78.5  86.7  75.2                                 Acrylic acid ester                                                                         19.5    23.0    19.1  13.2  24.6                                 Maleic anhydride                                                                            1.4     1.7     2.4   0.11  0.12                                MI of polymer                                                                               0.8     32      2.3   2.1   45                                  (g/10 min)                                                                    ______________________________________                                         *MMA: methyl methacrylate                                                

                                      TABLE 2                                     __________________________________________________________________________                      Amount     Curing conditions                                                                              Tensile test                                      (%) of     Temper-                Strength                                                                           Elonga-                     Modifier   bound      ature Pressure                                                                           Time  100%  at break                                                                           tion at              Polymer                                                                              Kind*.sup.2                                                                        Amount*.sup.1                                                                       modifier                                                                            Recipe*.sup.3                                                                      (°C.)                                                                        (kg/cm.sup.2)                                                                      (minutes)                                                                           Modulus                                                                             (kg/cm.sup.2)                                                                      break                __________________________________________________________________________                                                             (%)                  Example 1                                                                            O    1     64    A    170   60   30    29    135  750                  Example 1                                                                            O    2     91    A    170   60   30    31    167  600                  Example 1                                                                            L    2     73    A    190   60   30    28    130  630                  Example 1                                                                            O    1     64    B    190   100  30    33    195  650                  Example 2                                                                            O    1     70    A    170   60   30    27    137  680                  Example 2                                                                            E    2     85    B    170   60   60    34    180  550                  Example 3                                                                            O    1     63    B    190   100  30    27    175  650                  Example 3                                                                            D    3     95    A    190   70   60    28    220  550                  Example 3                                                                            A    1     55    B    170   70   60    25    110  800                  Comparative                                                                          O    1     60    B    190   100  30    29    65   950                  Example 1                                                                     Comparative                                                                          D    2     65    B    190   100  30    30    57   880                  Example 1                                                                     Comparative                                                                          O    2     85    A    "     "    "     22    43   900                  Example 2                                                                     Comparative                                                                          E    3     53    B    "     "    "     24    40   >1000                Example 2                                                                     __________________________________________________________________________                                                      Elongation                                                                          Izod impact                                                       Tension                                                                             (%) after                                                                           strength                                                   Shore  permanent                                                                           190° C.                                                                      at -70°                                                                C.                                                  Polymer                                                                              hardness (A)                                                                         set (%)                                                                             70 hours                                                                            (kg ·                                                                cm/cm)                __________________________________________________________________________                                  Example 1                                                                            63     6     410   87                                                  Example 1                                                                            64     5     380   92                                                  Example 1                                                                            63     6     390   75                                                  Example 1                                                                            66     7     380   77                                                  Example 2                                                                            63     7     375   65                                                  Example 2                                                                            70     5     320   70                                                  Example 3                                                                            64     4     365   80                                                  Example 3                                                                            73     8     310   43                                                  Example 3                                                                            62     10          75                                                  Comparative                                                                          77     53    600    4                                                  Example 1                                                                     Comparative                                                                          73     47    570    7                                                  Example 1                                                                     Comparative                                                                          52     43    500    3                                                  Example 2                                                                     Comparative                                                                          55     37    650    8                                                  Example 2                                       __________________________________________________________________________    Note                                                                          *.sup.1 1: one mole per mole of maleic anhydride                              2: two moles per mole of maleic anhydride                                     3: three moles per mole of maleic anhydride                                   *.sup.2 O: oleyl amine                                                        D: 1-amino-5-dodecene                                                         L: lauryl alcohol                                                             E: 1-hydro-9-octadecene                                                       A: allyl alcohol                                                              *.sup.3                                                                         Recipe    A(PHR)                                                                             B(PHR)                                                         sulfur    1      1.5                                                          Nocceler M                                                                              5    5                                                              Nocceler TT                                                                               0.5                                                                                0.5                                                          ZnO (zinc oxide)                                                                        1    1                                                              SRF (carbon black)                                                                      35   50                                                             DOS (plasticizer)                                                                       5    10                                                             stearic acid                                                                            1    1                                                              Irganox 1010                                                                              0.5                                                                                0.5                                                    

EXAMPLES 4 AND 5 (Hydrolysis of Ethylene Copolymer (1))

20 g of a terpolymer comprising 79 mole% of ethylene, 18.5 mole% ofmethyl acrylate and 1.5 mole% of maleic anhydride (having an MI of 220g/10 min; hereinafter referred to as "copolymer (1)") was dissolved in200 ml of toluene. To the solution were added 100 ml of water andtriethyl amine in an amount of 3 moles per mole of maleic anhydride inthe copolymer. The mixture was heated (hydrolyzed) at 80° C. for 5 hourswith stirring. Then, hydrochloric acid was added to effectneutralization, and hydrochloric acid was further added so that thereaction mixture became weakly acidic. The mixture was allowed to standovernight. Then, hexane was added as a precipitating solvent toprecipitate the formed polymer. Hexane was exchanged with fresh hexaneseveral times to wash the polymer, and the polymer was vacuum-dried at40° C. overnight. The hydrolysis ratio was calculated from decrease ofthe absorption at 1,760 cm⁻¹, attributed to the acid anhydride, in theinfrared absorption spectrum (the same method was adopted in thesubsequent examples). It was found that the hydrolysis ratio was 100%.

(Modification with Unsaturated Amine or Unsaturated Alcohol)

Oleyl amine was added to the hydrolyzed copolymer in an amount of 0.5mole per mole of the dicarboxyl group in the thus-obtained hydrolysisproduct of the copolymer (1), and reaction was carried out whilekneading the mixture at 120° C. and 40 rpm for 20 minutes in alaboratory plastomill. Oleyl amine was reacted at a ratio of 84% of thetheoretical value (Example 4).

By using oleyl alchol in an amount of 1.0 mole per mole of thedicarboxyl group in the hydrolysis product of the copolymer (1) insteadof oleyl amine used in Example 4, the reaction was carried out whileconducting kneading under the same conditions as described in Example 1.Oleyl alcohol was reacted at a ratio of 76% of the theoretical value(Example 5).

EXAMPLES 6 AND 7 (Half Esterification of Copolymer (2))

20 g of a terpolymer comprising 72.2 mole% of ethylene, 26.8 mole% ofmethyl acrylate and 1.0 mole% of maleic anhydride (having an MI of 9.1g/10 min; hereinafter referred to as "copolymer (2)") was dissolved in200 ml of toluene, and 100 ml of methyl alcohol and 1 ml of triethylamine were added to the solution and reaction was carried out for 6hours under reflux of methanol. Then, the half-esterified polymer waswashed and dried in the same manner as in the case of the hydrolysisproduct of the ethylene copolymer (1). From the result of the infraredabsorption spectrum analysis conducted in the same manner as describedabove, it was found that the half esterification ratio was 60%.

(Modification with Unsaturated Amine or Unsaturated Alcohol)

The thus-obtained half-esterified product of the copolymer (2) wasmodified with oleyl amine (Example 6) or oleyl alcohol (Example 7) inthe same manner as described in Example 4 or Example 2. The conversionswere 85% and 78%, respectively.

EXAMPLES 8 AND 9 (Half Esterification of Copolymer (3))

A terpolymer comprising 83 mole% of ethylene, 15.5 mole% of ethylacrylate and 1.5 mole% of maleic anhydride (having an MI of 212 g/10min; hereinafter referred to as "copolymer (3)") was half-esterified,washed and dried in the same manner as described above with respect tothe copolymer (2). It was found that the copolymer (3) washalf-esterified at a ratio of 80%.

(Modification with Unsaturated Amine or Unsaturated Alcohol)

The thus-obtained half esterification product of the copolymer (3) wasmodified with oleyl amine (Example 8) or oleyl alcohol (Example 9) inthe same manner as described in Example 4 or Example 2. The conversionswere 87% and 72%, respectively.

A copolymer comprising 90 mole% of ethylene and 10 mole% of methylmethacrylate (having an MI of 250 g/10 min) was used instead of thecopolymer (1) used in Example 4, and oleyl amine was added and reactionwas carried out in the same manner as described in Example 4 (since thecopolymer did not contain a maleic anhydride group, the copolymer wasnot hydrolyzed nor reacted with oleyl amine) (Comparative Example 3).

A copolymer comprising 74 mole% of ethylene and 26 mole% of methylmethacrylate (having MI of 94 g/10 min) was used instead of thecopolymer (2) used in Example 6, and oleyl amine was added and reactionwas carried out in the same manner as described in Example 6 (for thereason described with respect to Comparative Example 3, the copolymerwas not hydrolyzed nor reacted with oleyl amine) (Comparative Example4).

A copolymer comprising 79 mole% of ethylene, 11 mole% of methylmethacrylate and 10 mole% of maleic anhydride (having an MI of 300 g/10min) was used instead of the copolymer (1) used in Example 4, andhydrolysis, neutralization, washing and drying were carried out in thesame manner as described in Example 4. The hydrolysis ratio was 100%. Inthe same manner as described in Example 4, oleyl amine was added to thehydrolyzed polymer and reaction was carried out. Oleyl amine was reactedat a ratio of 80% of the theoretical value (Comparative Example 5).

A copolymer comprising 96.7 mole% of ethylene, 1.0 mole% of methylmethacrylate and 2.3 mole% of maleic anhydride (having an MI of 6.7 g/10min) was used instead of the copolymer (1) used in Example 4, andhydrolysis, neutralization, washing and drying were carried out in thesame manner as described in Example 4. The hydrolysis ratio was 100%.The hydrolyzed polymer was reacted with oleyl amine under the sameconditions as described in Example 4. Oleyl amine was reacted at a ratioof 80% of the theoretical value (Comparative Example 6).

(Evaluation of Physical Properties)

Into 100 parts by weight of the thus-obtained modified ethylenecopolymer were incorporated amounts shown in Table 3 of powdery sulfurcapable of passing through a 200-mesh sieve (hereinafter referred to as"S"), tetramethylthiuram disulfide as the curing promoter (hereinafterreferred to as "TT"), 2-mercaptobenzothiazole as the curing promoter(hereinafter referred to as "M"), dipentamethylenethiuram tetrasulfideas the sulfur donor (hereinafter referred to as "TRA"), zinc oxide asthe curing promoting assistant, stearic acid as the curing promotingassistant andtetrakis(methylene-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)methane(Irganox 1010) as the antioxidant (hereinafter referred to as "1010"),and the resulting mixture was kneaded at room temperature by a two-rollmill. The obtained kneaded mixture was press-cured at 150° C. under apressure of 60 kg/cm² for 40 minutes. The cured product was subjected tothe tensile test and heat resistance test and the Shore hardness (A) andpermanent elongation were determined. The obtained results are shown inTable 4.

                  TABLE 3                                                         ______________________________________                                                  Mixing ratio                                                                  (parts by weight)                                                               Recipe       Recipe  Recipe                                       Additives   A            B       C                                            ______________________________________                                        Powdery sulfur                                                                            2.0          2.0     0                                            TT          2.0          1.0     0                                            M           1.0          0.5     0                                            TRA         0            0       5.0                                          Zinc oxide  5.0          5.0     5.0                                          Stearic acid                                                                              2.0          2.0     2.0                                          1010        0.5          0.5     0.5                                          ______________________________________                                    

Note, when the tension permanent set of the test piece obtained inComparative Example 3 was measured, the elongation was not restored tothe original state. When the test pieces obtained in ComparativeExamples 3 and 4 were subjected to the aging test, the test pieces weremolten.

                                      TABLE 4                                     __________________________________________________________________________                                               Heat                                                                          resistance                                    Tensile test              Tension                                                                             test                                          100% 300% Strength                                                                           Elongation                                                                          Shore                                                                              permanent                                                                           (elonga-                                      Modulus                                                                            Modulus                                                                            at break                                                                           at break                                                                            hardness                                                                           set   tion)                                     Recipe                                                                            (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (%)   (A)  (%)   (%)                                __________________________________________________________________________    Example 4                                                                            A   15   28   142  690   66   13    590                                       C   14   27   140  700   65   12    650                                Example 5                                                                            A   14   26   110  740   65   13    670                                Example 6                                                                            A    8   17   128  700   60    7    650                                       A   10   23   134  680   62    9    630                                       B    9   20   110  650   59    8    620                                       C    7   17    98  650   58    7    630                                Example 7                                                                            A    8   17   128  720   59    7    650                                Example 8                                                                            A   18   29   145  660   69   15    550                                       B   19   32    99  670   70   17    570                                Example 9                                                                            A   18   29    78  620   69   18    550                                       B   16   27    69  650   69   19    560                                Comparative                                                                          A   20   19    17  270   69   140   --                                 Example 3                                                                     Comparative                                                                          A    4   42    4   2500  43   2000  --                                 Example 4                                                                     Comparative                                                                          A   34   50    60  430   45   80    350                                Example 5                                                                     Comparative                                                                          A   68   82   246  540   72   300   480                                Example 6                                                                     __________________________________________________________________________     Note: *Curing time was 60 minutes.                                       

EXAMPLE 10

An ethylene/methyl methacrylate/methacrylic acid copolymer C-1 having acomposition shown in Table 5, which was prepared by partiallyhydrolyzing an ethylene/methyl methacrylate copolymer, was mixed with amodifier (oleyl amine) in an amount equimolar to the methacrylic acidunits, and the mixture was kneaded and reacted in a laboratoryplastomill at 140° C. and 40 rpm for 20 minutes. The ratio of thereaction between oleyl amine and the acid (Table 6) was 63.7%. Then, themodified polymer was mixed with a curing agent and curing assistant of arecipe shown in Table 6 and the mixture was kneaded under conditionswherein the copolymer could be kneaded. Then, the kneaded compositionwas press-cured under conditions shown in Table 6.

The physical properties of the cured product are shown in Table 6.

EXAMPLES 11 THROUGH 13

In the same manner as described in Example 10, an ethylene/methylacrylate/acrylic acid copolymer C-2 having a composition shown in Table5 was treated and cured under conditions (modifiers, amounts, recipesand curing conditions) shown in Table 6. The physical properties areshown in Table 6. Note, in the modification with oleyl alcohol inExample 13, 0.01 part by weight of p-toluene-sulfonic acid was used as acatalyst.

EXAMPLES 14 THROUGH 16 AND COMPARATIVE EXAMPLE 7

An ethylene/methyl methacrylate copolymer (MI=109 g/10 min) containing20% by weight of methyl methacrylate was mixed with 2 PHR of maleicanhydride under kneading (185° C., 40 rpm) in a laboratory plastomill,and then 0.25 PHR of dicumyl peroxide was added dividedly as 5 portionsand the mixture was kneaded for 10 minutes to obtain a maleicanhydridegrafted copolymer C-3. The amount grafted of maleic anhydridewas 1.35% by weight as the content.

This copolymer C-3 was modified and cured in the same manner as inExamples 10 through 13. The reaction conditions and physical propertiesare shown in Table 6.

EXAMPLE 17

A maleic anhydride-grafted copolymer C-4 was used in the same manner asdescribed in Example 14 except that an ethylene/methyl methacrylatecopolymer having a methyl methacrylate content of 48.0% by weight wasused as the base polymer. The thus-obtained polymer was modified andcured in the same manner as described in Example 10. The physicalproperties are shown in Table 6.

EXAMPLE 18 AND COMPARATIVE EXAMPLE 8

An ethylene/methyl methacrylate/glycidyl methacrylate copolymer C-5having a composition shown in Table 5 or an ethylene/glycidylmethacrylate copolymer C-5- Comparison having a composition shown inTable 5 was modified and cured in the same manner as described inExample 10. The obtained results are shown in Table 6.

EXAMPLES 19 AND 20 AND COMPARATIVE EXAMPLES 9 AND 10

An ethylene/methyl methacrylate/maleic anhydride copolymer C-6 having acomposition shown in Table 5 or an ethylene/methylmethacrylate/monoethyl maleate copolymer C-7 having a composition shownin Table 5 was reacted with oleyl amine in the same manner as describedin Example 10. The amount of oleyl amine reacted was equimolar to themaleic anhydride groups, and the conversion was 85% or 87%. Thethus-obtained oleyl amine-modified copolymer was mixed with 2 PHR ofdicumyl peroxide, and the mixture was kneaded at 100° C. and 40 rpm for3 minutes. The kneaded composition was press-crosslinked underconditions shown in Table 7. The physical properties of thethus-obtained crosslinked product are shown in Table 7 (Examples 19 and20). When the peroxide was not added, the polymer was not crosslinkedand was molten even at 110° C. (Comparative Examples 9 and 10).

EXAMPLE 21

An ethylene/methyl acrylate/octadecenyl acrylate copolymer C-8 having acomposition shown in Table 5 was modified and cured in the same manneras described in Example 10. Conditions, mixing ratios and physicalproperties are shown in Table 7.

EXAMPLE 22

An ethylene/methyl acrylate/maleic anhydride copolymer C-9 having acomposition shown in Table 5 and oleyl amine in an amount equimolar tothe maleic anhydride groups in the copolymer C-9 were dissolved intoluene, and the solution was refluxed for 2 hours. The solution wasadded to methanol to precipitate a polymer. The polymer was recovered byfiltration and the solvent was removed by evaporation. The conversionwas 87%. The modified copolymer was cured under additive and curingconditions shown in Table 7. The physical properties are shown in Table7.

EXAMPLE 23

The modified copolymer obtained in Example 22 was allowed to stand in anatmosphere maintained at 200° C. for 6 hours. By this operation, animide structure was formed and the physical properties and heatresistance of the cured product were improved Absorptions at 1640 cm⁻¹and 1540 cm⁻¹, attributed to the amide, disappeared, and an absorptionof the imide appeared at 1700 cm⁻¹.

COMPARATIVE EXAMPLE 11

The copolymer C-9 was modified with stearyl amine, which is a saturatedamine, in the same manner as described in Example 22. Curing of thepolymer was attempted under additive and curing conditions shown inTable 7, but the polymer could not be cured (molten at 110° C.).

                                      TABLE 5                                     __________________________________________________________________________    Compolymer      Content                                                                            Second                                                                              Content           MI                               No.    Third comonomer                                                                        (mole %)                                                                           comonomer                                                                           (mole %)                                                                           Remarks      (g/10 min)                       __________________________________________________________________________    C-1    MAA      0.95 MMA    5.7              109                              C-2    AA       1.2  MA    25.0              45.2                             C-3    MAH      0.46 MMA    6.6 MAH grafted to E/MMA                                                                        3.6                                    (grafted)                copolymer                                     C-4    MAH      0.67 MMA   20.9 MAH grafted to E/MMA                                                                        7.3                                    (grafted)                copolymer                                     C-5-   GMA      12.2 --    0                  3.0                             Comparison                                                                    C-5    GMA      2.3  MMA   20.7              12.3                             C-6    MAH      1.4  MMA    6.9              64.3                             C-7    MAH      1.0  MA    30.1              10.3                                    monoethyl ester                                                        C-8    Octadecenyl                                                                            0.27 MA    25.9 Octadecenyl acrylate                                                                       55.2                                    acrylate                 directly copolymerized                        C-9    MAH      0.97 MA    28.3               9.1                             __________________________________________________________________________     MAA: methacrylic acid                                                         MMA: methyl methacrylate                                                      MA: methyl acrylate                                                           AA: acrylic acid                                                              MAH: maleic anhydride                                                         GMA: glycidyl methacrylate                                                    E: ethylene                                                              

                                      TABLE 6                                     __________________________________________________________________________               Modifier         Curing conditions                                                                           Tensile test                               Co-          Con-    Temper-                                                                            Time                                                                              Pres-                                                                              100% 300% Strength                                                                           Elonga-                     poly-                                                                             Kind                                                                              Amount                                                                             version                                                                           Recipe                                                                            ature                                                                              (min-                                                                             sure Modulus                                                                            Modulus                                                                            at break                                                                           tion at                     mer *1  *2   *3 (%)                                                                            *4  (°C.)                                                                       utes)                                                                             (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      break                __________________________________________________________________________                                                             (%)                  Example 10                                                                           C-1 OAm 1.0    63.7                                                                            A   150  40  60   50.9 57.4  87.6                                                                              580                  Example 11                                                                           C-2 OAm 1.0  68  A   "    "   "    12.2 35.6 120.7                                                                              660                  Example 12                                                                           C-2 OAm 1.0  68  C   "    "   "    10.2 25.8 135.2                                                                              630                  Example 13                                                                           C-2 OAl 1.0  53  A   "    "   "     9.8 25.3  85.0                                                                              720                  Example 14                                                                           C-3 OAm 0.9  85  A   "    "   "    47.5 58.1 123.1                                                                              630                  Example 15                                                                           C-3 OAm 0.9  85  C   "    "   "    49.2 55.4 130.1                                                                              610                  Comparative                                                                          C-3 OAm 0.0  --  A   "    "   "    43.6 45.6  49.5                                                                              300                  Example 7                                                                     Example 16                                                                           C-3 OA1 1.0  48  A   "    "   "    44.4 51.2 102.7                                                                              620                  Example 17                                                                           C-4 OAm 0.9  82  A   "    "   "    18.2 27.2 140.3                                                                              700                  Comparative                                                                          C-5-                                                                              MAA 0.4  65  B   150  30  60   72.0 102.5                                                                              182  720                  Example 8                                                                            Com-                                                                          pari-                                                                         son                                                                    Example 18                                                                           C-5 MAA 0.6  63  B   "    "   "    16.1 41.7 136.6                                                                              550                  __________________________________________________________________________                                           Tension                                                                Shore  permanent                                                                            Heat aging                                                      hardness (A)                                                                         set *5 (%)                                                                           test *6 (%)                                                                         Remarks                   __________________________________________________________________________                             Example 10                                                                           86     150    320   Saponification of                                                             copolymer                                          Example 11                                                                           60      14    390   Direct                                                                        copolymerization                                   Example 12                                                                           58      16    390                                                      Example 13                                                                           58      20    420                                                      Example 14                                                                           87     140    380   Grafting with maleic                                                          anhydride                                          Example 15                                                                           86     130    410                                                      Comparative                                                                          85     Measurement                                                                          Molten                                                   Example 7     impossible                                                      Example 16                                                                           87     150    370                                                      Example 17                                                                           60      21    400                                                      Comparative                                                                          92     400    390                                                      Example 8                                                                     Example 18                                                                           61      18    330                             __________________________________________________________________________     Note                                                                          *1 OAm: oleyl amine                                                           OAl: oleyl alcohol                                                            MAA: methacrylic acid                                                         DCP: dicumyl peroxide                                                         *2 moles per mole of second comonomer, but PHR in case of DCP                 *3 determined according to IR method                                          *4 Recipes (PHR)                                                              A: S(2), TT(2), M(1), ZnO(5), stearic acid(2)                                 B: S(2), TT(1), M(0.5), ZnO(5), stearic acid(2)                               C: TRA(5), Zno(5), stearic acid(2)                                            (Tetron A)                                                                    *5 Sample was elongated at ratio of 50% of elongation at break, maintaine     for 10 minutes and then shrunk, and elongation was measured after lapse o     10 minutes                                                                    *6 elongation after 190° C. for 70 hours                          

                                      TABLE 7                                     __________________________________________________________________________    (Peroxide curing)                                                             __________________________________________________________________________               Modifier         Curing conditions                                                                           Tensile test                               Co-          Con-    Temper-                                                                            Time                                                                              Pres-                                                                              100% 300% Strength                                                                           Elonga-                     poly-                                                                             Kind                                                                              Amount                                                                             version ature                                                                              (min-                                                                             sure Modulus                                                                            Modulus                                                                            at break                                                                           tion at                     mer *1  (PHR)                                                                              (%) Recipe                                                                            (°C.)                                                                       utes)                                                                             (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      break                __________________________________________________________________________                                                             (%)                  Example 19                                                                           C-6 DCP 2    --  --  170  30  60   40.5 48.5 80.0 610                  Comparative                                                                          C-6 --  0    --  --  170  30  60   34.0 35.0 37.5 640                  Example 9                                                                     Example 20                                                                           C-7 DCP 2    --  --  170  30  60    4.5  5.7 27.1 850                  Comparative                                                                          C-7 --  0    --  --  170  30  60    3.1  2.8  1.0 2900                 Example 10                                                                    Example 21                                                                           C-8 --  --   --  B   150  30  60   16.3 38.3 156  650                  Comparative                                                                          C-9 SAm 1.0      B   150  30  60    6.5  9.7 41.5 1450                 Example 11                                                                    Example 23                                                                           C-9 OAm 1.0      B   150  30  60   14.0 39.1 200.9                                                                              590                  Example 22                                                                           C-9 OAm 1.0      B   150  30  60   11.9 29.7 167.0                                                                              670                  __________________________________________________________________________                                          Tension                                                                Shore  permanent                                                                            Heat aging                                                      hardness (A)                                                                         set (%)                                                                              test (%)                                                                            Remarks                    __________________________________________________________________________                            Example 19                                                                           84     140    450   Crosslinking with                                                             OAm-peroxide                                       Comparative                                                                          82     280    Molten                                                   Example 9                                                                     Example 20                                                                           58     15     620   Crosslinking with                                                             OAm-peroxide                                       Comparative                                                                          42     Measurement                                                                          Molten                                                   Example 10    impossible                                                      Example 21                                                                           65     25     410   Direct                                                                        copolymerization                                   Comparative                                                                          520    Above  Molten                                                                              Not cured                                          Example 11    1000                                                            Example 23                                                                           59     11     490   Imide modification                                 Example 22                                                                           60     15     410   Amide                      __________________________________________________________________________                                                       modification                Note                                                                          *1 DCP: dicumyl peroxide                                                      SAm: stearyl amine                                                            OAm: oleyl amine                                                         

We claim:
 1. A cured produce prepared by curing a random multiplexethylene copolymer comprising (a) 53 to 86.6 mole% of units derived fromethylene, which are represented by the following formula (I):

    --CH.sub.2 --CH.sub.2 --tm (I)

(b) 5 to 45 mole% of units derived from a monomer selected from alkylacrylates, alkyl methacrylates, vinyl carboxylates and isopropenylcarboxylates, which are represented by the following formula (II):##STR16## wherein R₁ stands for a hydrogen atom or a methyl group, and Xis ##STR17## in which R₂ and R₃ stand for an alkyl group having 1 to 10carbon atoms), and (c) 0.2 to 5 mole% of units derived from a monomerhaving a radical-polymerizable ethylenic double bond and at least onecarbon-to-carbon double bond which is different from a double bond of anaromatic nucleus, with at least one curing agent selected from sulfur,sulfur donors and peroxides, wherein the units (c) derived from theradical-polymerizable monomer are represented by the following formula(III): ##STR18## wherein R₄ stands for a hydrogen atom or ##STR19## (inwhich R₆ stands for a hydrogen atom or an alkyl group having 1 to 6carbon atoms), R₇ stands for a hydrogen atom or a methyl group, R₈stands for a hydrocarbon residue having at least one carbon-to-carbondouble bond different from a double bond of an aromatic nucleus andhaving up to 40 carbon atoms, and Y is a divalent group selected fromdivalent groups represented by the following formulas (IV) through (IX):##STR20## wherein Q in the formulae (VIII) and (IX) is ##STR21## and R₉in the formula (VII) and the definition of Q stands for a hydrocarbonresidue having at least one carbon-to-carbon double bond different froma double bond of an aromatic nucleus and up to 40 carbon atoms, analkyl, aryl or aralkyl group having up to 20 carbon atoms or a hydrogenatom, wherein said random multiplex ethylene copolymer is prepared byone of the following three processes: (i) a process comprisingpolymerizing a monomer mixture comprised of (a) ethylene, (b) themonomer for forming the units represented by the formula (II), and (c)the monomer having a radical-polymerizable ethylenic double bond and atleast one carbon-to-carbon double bond which is different from a doublebond of an aromatic nucleus: (ii) a process comprising polymerizing amonomer mixture comprised of (a) ethylene, (b) the monomer for formingthe units represented by the formula (II), and (c) the monomer having aradical-polymerizable ethylenic double bond and a functional groupselected from the group consisting of an acid anhydride group, acarboxyl group and an epoxy group, and modifying the thus-obtainedcopolymer with a low molecular-weight modifier having an amino group, ahydroxyl group or a carboxyl group which are capable of reacting withthe functional group to introduce a carbon-to-carbon double bond in sidechains of the copolymer, and (iii) a process comprising polymerizing amonomer mixture comprised of (a) ethylene and (b) the monomer forforming the units represented by the formula (II), graft-polymerizingthe monomer having a radical-polymerizable ethylenic double bond and afunctional group selected from the group consisting of an acid anhydridegroup, a carboxyl group and an epoxy group, onto thus-obtainedcopolymer, and modifying the thus-obtained graft-copolymer with a lowmolecular-weight modifier having an amino group, a hydroxyl group or acarboxyl group which are capable of reacting with the functional groupto introduce a carbon-to-carbon double bond in side chains of thecopolymer.
 2. A cured product prepared by curing a random multiplexethylene copolymer comprising (a) 53 to 86.6 mole% of units derived fromethylene, which are represented by the following formula (I):

    --CH.sub.2 --CH.sub.2 --                                   (I)

(b) 5 to 45 mole% of units derived from a monomer selected from alkylacrylates, alkyl methacrylates, vinyl carboxylates and isopropenylcarboxylates, which are represented by the following formula (II):##STR22## wherein R₁ stands for a hydrogen atom or a methyl group, and Xis ##STR23## (in which R₂ and R₃ stand for an alkyl group having 1 to 10carbon atoms), and (c) 0.2 to 5 mole% of units derived from a monomerhaving a radical-polymerizable ethylenic double bond and at least onecarbon-to-carbon double bond which is different from a double bond of anaromatic nucleus, with at least one curing agent selected from sulfur,sulfur donors and peroxides, wherein the units (c) derived from theradical-polymerizable monomer are selected from units represented by thefollowing formulae (X), (XI), (XII) and (XVI); ##STR24## wherein R₇ andR₁₀ stand for a hydrogen atom or a methyl group, R₁₁ stands for ahydrocarbon residue having a carbon-to-carbon double bond different froma double bond of an aromatic nucleus and having 6 to 20 carbon atoms,R₁₂ stands for a hydrogen atom or an alkyl group having 1 to 10 carbonatoms, and Z and Z' independently stand for ##STR25## wherein saidrandom multiplex ethylene copolymer is prepared by one of the followingthree processes: (i) a process comprising polymerizing a monomer mixturecomprised of (a) ethylene, (b) the monomer for forming the unitsrepresented by the formula (II), and (c) the monomer having aradical-polymerizable ethylenic double bond and at least onecarbon-to-carbon double bond which is different form a double bond of anaromatic nucleus: (ii) a process comprising polymerizing a monomermixture comprised of (a) ethylene, (b) the monomer for forming the unitsrepresented by the formula (II), and (c) the monomer having aradical-polymerizable ethylenic double bond and a functional groupselected from the group consisting of an acid anhydride group, acarboxyl group and an epoxy group, and modifying the thus-obtainedcopolymer with a low molecular-weight modifier having an amino group, ahydroxyl group or a carboxyl group which are capable of reacting withthe functional group to introduce a carbon-to-carbon double bond in sidechains of the copolymer, and (iii) a process comprising polymerizing amonomer mixture comprised of (a) ethylene and (b) the monomer forforming the units represented by the formula (II), graft-polymerizingthe monomer having a radical-polymerizable ethylenic double bond and afunctional group selected from the group consisting of an acid anhydridegroup, a carboxyl group and an epoxy group, onto thus-obtainedcopolymer, and modifying the thus-obtained graft-copolymer with a lowmolecular-weight modifier having an amino group, a hydroxyl group or acarboxyl group which are capable of reacting with the functional groupto introduce a carbon-to-carbon double bond in side chains of thecopolymer.